JPH11166091A - Vinyl chloride-based resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a vinyl chloride-based resin composition that improves the gelation properties of a vinyl chloride-based resin, remarkably reduces the occurrence of an ungelled material and further remarkably improves the processability without deteriorating the transparency. SOLUTION: This composition comprises 100 pts.wt. vinyl chloride-based resin and 0.1-30 pts.wt. processing aid for the vinyl chloride-based resin. The processing aid for the vinyl chloride-based resin is a copolymer prepared by copolymerizing (B) 70-97 pts.wt. of a mixture of 60-100 wt.% of methyl methacrylate with 0-40 wt.% of one or monomers in an alkyl acrylates and alkyl methacrylates except the methyl methacrylate and 0-10 wt.% of a vinylic monomer copolymerizable therewith in the presence of a latex obtained by carrying out the emulsion copolymerization of (A) 3-30 pts.wt. of a mixture of 0-50 wt.% of the methyl methacrylate with 50-100 wt.% of the alkyl acrylate and 0-20 wt.% of the vinylic monomer copolymerizable therewith. The copolymer has >=1 specific viscosity of a solution prepared by dissolving 0.4 g of the copolymer in 100 mL of benzene at 30 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vinyl chloride resin composition which gives a molded article having excellent workability and excellent physical properties. More specifically, the present invention relates to a vinyl chloride resin composition comprising a vinyl chloride resin and a processing aid for a vinyl chloride resin mainly containing a polymer of methyl methacrylate and another alkyl methacrylate and alkyl acrylate. .

[0002]

2. Description of the Related Art Vinyl chloride resins are widely used in various fields to provide molded articles having excellent physical and chemical properties. However, since the processing temperature is close to the thermal decomposition temperature, there are various processing problems such as a narrow temperature range in which molding is possible and a long time until the molten state.

[0003] Many techniques are known today that attempt to overcome the above processing problems. Typical technologies include
For example, techniques such as adding a plasticizer to a vinyl chloride resin, using a vinyl chloride resin obtained by copolymerizing another monomer with vinyl chloride, and mixing other resin components with the vinyl chloride resin are known. I have.

However, none of these techniques can sufficiently improve the processability while maintaining the excellent physical properties and chemical properties inherent in the vinyl chloride resin. For example, when a plasticizer is added to a vinyl chloride resin or a vinyl chloride-based resin obtained by copolymerizing another monomer with vinyl chloride is used, the physical properties of the molded article change significantly. In many cases where other resin components are mixed with the vinyl chloride resin, the melt viscosity at the time of molding is lowered, and thus the processing temperature is lowered. Although these methods apparently improve the flowability of the vinyl chloride resin,
In practice, the kneading energy is consumed by the flow, and the gelation of the vinyl chloride resin becomes insufficient. Therefore, even if it is apparently transparent, its physical properties are inferior to those of a sufficiently gelled vinyl chloride resin.

In order to solve the above-mentioned problems, Japanese Patent Publication No. 40-5311 proposes a method in which a copolymer having a relatively high molecular weight of methyl methacrylate as a main component is blended as a processing aid. However, the added processing aid tends to remain as an ungelled substance (generally called fisheye), which easily impairs the appearance of the product, improves the product gloss, improves the secondary workability, There is a problem that the effect of adding other processing aids, such as a decrease in specific gravity during foam molding, is not sufficiently exhibited.

JP-B-52-49020 and JP-B-5-49020
In the presence of a latex of a polymer of methyl methacrylate or a copolymer containing a significant amount of methyl methacrylate disclosed in Japanese Patent Application Laid-Open No. 3-2898, a methacrylate ester other than a acrylate or methyl ester of a dominant amount is polymerized. The method of blending the two-stage polymer as a processing aid has a certain effect in preventing the generation of the ungelled product, but is not sufficient, and when added to a vinyl chloride-based resin, the transparency of the molded product is reduced. In many cases, phenomena presumed to be caused by insufficient dispersing of the processing aid in the vinyl chloride-based resin, such as a decrease in the degree of gelation, a decrease in the degree of gelation, and a decrease in secondary workability such as high-temperature elongation, often occur.

It can be easily inferred that the use of a processing aid having a high molecular weight will increase the effect of imparting viscosity and elasticity to the vinyl chloride resin.

[0008] However, it is well known that a simple increase in the molecular weight of the processing aid causes a significant decrease in dispersion as described above.

In order to prevent the generation of ungelled substances and improve the transparency in such a high molecular weight region, Japanese Patent No. 2515014 discloses a component containing a predominant amount of methyl methacrylate followed by a component containing a predominant amount of alkyl acrylate. A method is disclosed in which the latex particle diameter of the added and polymerized two-stage polymer is 1000 ° or less.

[0010] A technique of using a component mainly composed of an acrylate ester having a relatively low glass transition temperature as a core of a two-stage polymer is disclosed in French Patent No. 2180595. The object of the present invention is to use a processing aid having a relatively low molecular weight to prevent sticking to a metal surface during processing and to increase the viscosity of a vinyl chloride resin and to exhibit the elasticity of a molten resin represented by the ballistic effect. However, this is based on a different idea from other conventional technologies, and this technology does not provide the effects such as improvement of workability obtained in the present invention.

[0011]

When a processing aid is added to a vinyl chloride resin and used, the generation of ungelled matter is as follows:
Not only is the effect of the addition of the processing aid not obtained, but also the transparency inherent in the vinyl chloride resin is lowered, and excellent physical and chemical properties are impaired. If the problem of dispersion reduction typified by generation of ungelled matter is solved, higher addition effect can be obtained by adding the same amount as the conventional one, and the addition amount to obtain the same effect can be reduced. Can be. Furthermore, since it is possible to suppress the deterioration of various physical properties due to the increase in the molecular weight of the processing aid,
It is possible to further increase the efficiency of the processing aid.

[0012]

SUMMARY OF THE INVENTION In view of the above-mentioned circumstances, the present invention improves the gelling property of a vinyl chloride resin by adding a smaller amount thereof, greatly reduces the generation of ungelled substances, and furthermore, improves the transparency. As a result of intensive studies on processing aids that do not lower and greatly improve processability, methyl methacrylate was used as the main component in the presence of a copolymer latex that was emulsion-polymerized with a monomer mixture containing alkyl acrylate as the main component. A polymer obtained by addition polymerization of a mixed monomer to be,
It has been found that the above object can be achieved by using a relatively high molecular weight as a processing aid, and the present invention has been completed.

That is, the present invention relates to a vinyl chloride resin 10
A composition comprising 0 parts (parts by weight, hereinafter the same) and 0.1 to 30 parts of a processing aid for a vinyl chloride resin, wherein the processing aid for the vinyl chloride resin is methyl methacrylate 0 to 30 parts.
50% (% by weight, hereinafter the same) and alkyl acrylate 50
To 100% and a vinyl monomer copolymerizable therewith.
20% of the mixture (A) in the presence of a latex obtained by emulsion polymerization of 3 to 30 parts of methyl methacrylate
A mixture of 100%, 0 to 40% of at least one monomer selected from alkyl methacrylate except alkyl acrylate and methyl methacrylate, and 0 to 10% of a vinyl monomer copolymerizable therewith. (B) A polymer obtained by adding and polymerizing 70 to 97 parts so that the total amount becomes 100 parts, wherein the specific viscosity at 30 ° C. of a solution obtained by dissolving 0.4 g of the polymer in 100 ml of benzene is 1 The vinyl chloride resin composition (Claim 1), wherein the latex of the polymer of the processing aid for the vinyl chloride resin has a particle size of 1000 ° or less. Vinyl chloride resin composition according to claim 2 (Claim 2)
About.

[0014]

DETAILED DESCRIPTION OF THE INVENTION The feature of the present invention is that emulsion polymerization is carried out as a first stage component using a copolymer obtained by polymerizing a conventionally used monomer mixture containing a predominant amount of methyl methacrylate, A monomer mixture containing a predominant amount of alkyl acrylate is added and replaced with a processing aid for a two-stage polymer obtained by polymerization, and the monomer mixture containing a predominant amount of alkyl acrylate is emulsion-polymerized and copolymerized. The method is to obtain a combined latex, then add a monomer mixture containing a predominant amount of methyl methacrylate, and use a processing aid from a polymer obtained by polymerization. The presence of the component containing the alkyl acrylate in the inner layer in a predominant amount can assist the dispersion of the component in the outer layer containing the predominant amount of the methyl methacrylate in the outer layer, which is a component similar to a normal vinyl chloride resin processing aid. The use of coalescing processing aids promotes gelation without impairing the excellent physical and chemical properties inherent in vinyl chloride resins, and improves secondary processability during foam molding. It has been found that the effects expected from the addition of processing aids, such as lowering the specific gravity of, and improving the gloss of products, can be remarkably exhibited by the addition of a small amount.

The vinyl chloride resin composition of the present invention is a composition comprising 100 parts of a vinyl chloride resin and 0.1 to 30 parts of a processing aid for the vinyl chloride resin.

The vinyl chloride resin is a polymer composed of 80 to 100% of vinyl chloride units and 0 to 20% of units of other monomers copolymerizable with vinyl chloride.

Other monomers copolymerizable with vinyl chloride include, for example, vinyl acetate, propylene, styrene, acrylate and the like. These may be used alone or in combination of two or more.

The average degree of polymerization of the vinyl chloride resin is not particularly limited, and any conventional vinyl chloride resin can be used.

Specific examples of such a vinyl chloride resin include, for example, polyvinyl chloride, 80% or more of a vinyl chloride monomer and other copolymerizable monomers (for example, vinyl acetate, propylene, styrene, acrylic Acid esters, etc.), and post-chlorinated polyvinyl chloride. These may be used alone or in combination of two or more.

The above-mentioned processing aid for vinyl chloride resin is a polymer obtained by adding and polymerizing the mixture (B) in the same system in the presence of a latex obtained by emulsion-polymerizing the mixture (A). In other words, the vinyl chloride resin is provided with excellent properties such as gelling property and processability without deteriorating properties such as excellent transparency.

The mixture (A) is a mixture comprising 0 to 50% of methyl methacrylate, 50 to 100% of alkyl acrylate, and 0 to 20% of a vinyl monomer copolymerizable therewith.

The vinyl monomers copolymerizable therewith are used if necessary, depending on the intended use of the vinyl chloride resin composition.

By arranging the copolymer obtained by polymerizing the mixture (A) in the inner layer of the polymer, when the processing aid is added to the vinyl chloride resin, the gelation is promoted,
The generation of ungelled matter can be prevented. As a result, the vinyl chloride resin can efficiently impart viscosity and elasticity.

Specific examples of the alkyl acrylate include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and the like. These may be used alone or in combination of two or more. Of these, butyl acrylate is preferred because it gives a polymer having a low glass transition temperature.

Specific examples of the vinyl monomers copolymerizable therewith include aromatic vinyls such as styrene and α-methylstyrene and unsaturated nitriles such as acrylonitrile. These may be used alone or in combination of two or more.

The proportion of each component of the mixture (A) is 0 to 50%, preferably 20 to 50% of methyl methacrylate,
More preferably, 30 to 45%, alkyl acrylate 5
0 to 100%, preferably 50 to 80%, more preferably 55 to 70%, and 0 to 20%, preferably 0 to 10%, more preferably 0 to 5% of a vinyl monomer copolymerizable therewith. Is a mixture consisting of If the proportion of methyl methacrylate in the mixture (A) exceeds 50%, good gelling properties will be lost or ungelled products will be generated. The same applies when the proportion of alkyl acrylate is less than 50%. Further, it is preferable not to use a vinyl monomer copolymerizable with the above for good gelling property which is a feature of the present invention, but it is preferable to use it within a range not exceeding 20% if necessary. Can be.

The mixture (B) contains methyl methacrylate 60
0 to 100% and 0 to 40% of at least one monomer selected from alkyl methacrylate except alkyl acrylate and methyl methacrylate, and a vinyl monomer copolymerizable with these if necessary It is a mixture with 0-10% of body. This component has the same action as the component which improves the gelling property and processability used in conventional processing aids for vinyl chloride.

If necessary, the above-mentioned vinyl monomers copolymerizable therewith are components used according to the purpose of use of the vinyl chloride resin composition.

Specific examples of the alkyl acrylate include methyl acrylate, ethyl acrylate, butyl acrylate and 2-ethylhexyl acrylate. Specific examples of the alkyl methacrylate excluding methyl methacrylate include, for example, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, and the like. These alkyl acrylates and alkyl methacrylates other than methyl methacrylate may be used alone or in combination of two or more.

Specific examples of the vinyl monomers copolymerizable therewith include, for example, aromatic vinyls such as styrene and α-methylstyrene and unsaturated nitriles such as acrylonitrile. These may be used alone or in combination of two or more.

The proportion of each component in the mixture (B) is 60 to 100%, preferably 60 to 90%, of methyl methacrylate.
Furthermore, 65 to 85%, 0 to 40%, preferably 0 to 30%, and more preferably 0 to 20% of at least one monomer selected from alkyl methacrylate except alkyl acrylate and methyl methacrylate. , And 0-10%, preferably 0-5%, of other copolymerizable vinyl monomers.
%, And further 0 to 3%.

When the proportion of methyl methacrylate in the mixture (B) is less than 60%, transparency, processability, etc., are reduced. If at least one monomer selected from alkyl methacrylates other than alkyl acrylate and methyl methacrylate exceeds 40%, transparency, processability, and the like are reduced. Further, when the amount of the other copolymerizable vinyl monomer exceeds 10%, gelling properties and transparency are reduced.

The content of the copolymer from the mixture (A) in 100 parts of the processing aid is 3 to 30 parts, preferably 5 to 20 parts, more preferably 8 to 15 parts. When the component is present in a small amount of 3 to 30 parts in the inner layer of the polymer, the gelling property and the processability are specifically improved, and as a result, the effect of adding the processing aid can be dramatically improved. it can.
It has not been known that such a small component has a specific effect. When the amount of the mixture (A) exceeds 30 parts, the gelling property and transparency of the vinyl chloride resin are impaired. When the amount is less than 3 parts, the dispersibility of the processing aid in the vinyl chloride resin is impaired.
Ungelled matter is generated.

The content of the copolymer from the mixture (B) in 100 parts of the processing aid is 70 to 97 parts, preferably 80 to 95 parts, more preferably 85 to 92 parts. When the amount of the component exceeds 97 parts, the dispersibility of the processing aid in the vinyl chloride resin is impaired, and an ungelled substance is generated.
On the other hand, if the amount is less than 70 parts, the desired gelation property of the present invention cannot be sufficiently improved.

The polymer can be produced, for example, by the following method.

First, the mixture (A) is mixed with a suitable medium, an emulsifier,
Emulsion polymerization is carried out in the presence of a polymerization initiator and a chain transfer agent to obtain a polymer latex of the mixture (A). Then, the mixture (B) is sequentially added to the polymer latex of the mixture (A) to carry out polymerization. By sequentially polymerizing the respective mixtures in this manner, the polymer of the mixture (A) forms an inner layer, and the polymer of the mixture (B) forms a polymer forming an outer layer.

The medium used in the emulsion polymerization is usually water.

As the emulsifier, known emulsifiers may be used, for example, fatty acid salts, alkyl sulfate salts,
Examples thereof include anionic surfactants such as alkyl benzene sulfonate, alkyl phosphate ester salt, and sulfosuccinic acid diester salt, and nonionic surfactants such as polyoxyethylene alkyl ether and polyoxyethylene fatty acid ester.

As the polymerization initiator, a water-soluble or oil-soluble polymerization initiator, a thermal decomposition type or redox type polymerization initiator and the like are used. For example, a usual inorganic initiator such as persulfate, or an organic peroxide is used. Or an azo compound alone or in combination with the above compound and a sulfite, a hydrogen sulfite, a thiosulfate, a first metal salt, sodium formaldehyde sulfoxylate, or the like, and may be used in a redox system. Preferred persulfates as the polymerization initiator include, for example, sodium persulfate, potassium persulfate, ammonium persulfate, and the like. Preferred organic peroxides include
For example, t-butyl hydroperoxide, cumene hydroperoxide, benzoyl peroxide, lauroyl peroxide and the like can be mentioned.

The polymerization temperature and time are not particularly limited, and may be suitably adjusted according to the purpose of use so as to obtain a desired specific viscosity and particle diameter.

The latex of the polymer of the processing aid thus obtained has an average particle diameter of 100 to 3000.
{, More preferably 100 to 1000}. It is difficult to obtain a latex having an average particle size of less than 100 °,
When the temperature exceeds 3000 °, the dispersibility decreases, and when the temperature is 1000 ° or less, molding tends to be performed under severe processing conditions.

The dispersing performance of the processing aid may be determined under normal conditions (for example, when a normal tin compound is used) under processing conditions (roll temperature, etc.) and types of compounds such as stabilizers and lubricants. Good workability is exhibited at a roll temperature of about 160 to 180 ° C. when processed with an 8-inch test roll. However, even within the scope of the present invention,
Depending on the conditions, for example, when the roll temperature is low (for example, when the roll temperature is 140 to 160 ° C.) or when the amount of the blended lubricant is large, the dispersing performance decreases,
Gelation is difficult to progress, and transparency and processability may be reduced. In such a case, the average particle diameter of the latex of the processing aid is changed to the above range, and the average particle diameter is 1,000 ° or less.
The above problem can be improved by setting the temperature to preferably 800 ° or less and preferably 100 ° or more.

The latex in the above range can be used under the above-mentioned ordinary conditions without any particular problem.

The polymer latex of the processing aid obtained as described above is subjected to salting out by adding a usual electrolyte,
It is used by separating from latex by coagulation or spraying and drying in hot air.

The obtained two-stage polymer can be subjected to washing, dehydration, drying, and other treatments as required by a usual method.

The obtained processing aid is usually preferably in the form of a white powder having an average particle diameter of 30 to 300 μm.

0.4 g of the above-mentioned processing aid used in the present invention is dissolved in 100 ml of benzene, and the specific viscosity measured at 30 ° C. is 1 or more, preferably 1.2 or more, more preferably 1. 5 or more, 7 or less, further 5 or less,
In particular, it is preferably 3 or less. If it is less than 1, sufficient workability cannot be obtained. On the other hand, if it exceeds 7, the transparency tends to decrease.

0.4 g of processing aid in 100 ml of benzene
When the specific viscosity measured at 30 ° C. becomes 1 or more, the gelling property of the vinyl chloride resin decreases or the high temperature elongation occurs when the conventional processing aid is added to the vinyl chloride resin. There are problems such as a decrease in workability such as a decrease in specific gravity during foam molding. However, the processing aid used in the present invention has sufficient gelling properties and processability even at a high molecular weight such that the specific viscosity is 1 or more, and a high molecular weight processing aid is inherently used. High ability can be fully developed.

The vinyl chloride resin composition of the present invention can be obtained by mixing the above-mentioned processing aid with the above-mentioned vinyl chloride resin according to a usual method.

The mixing ratio of the vinyl chloride resin and the processing aid for the vinyl chloride resin is as follows.
The processing aid for vinyl chloride-based resin 0.1
To 30 parts, preferably 0.3 to 10 parts, more preferably 0.5 to 5 parts. When the amount of the processing aid for the vinyl chloride resin is less than 0.1 part, the effect of adding the processing aid cannot be sufficiently obtained, and when the amount exceeds 30 parts, the excellent mechanical properties of the vinyl chloride resin are impaired. .

The vinyl chloride resin composition of the present invention thus obtained may contain, if necessary, a stabilizer, a lubricant, an impact resistance enhancer, a plasticizer, a coloring agent, a filler, a foaming agent and the like. May be used.

The vinyl chloride resin composition of the present invention is excellent in processability and can be formed by a method such as blow molding, injection molding, calender molding, or extrusion molding. The resulting molded article has excellent properties such as transparency, gloss, surface smoothness, etc. and excellent secondary workability, and when used for foam molding, it has excellent properties such as a low specific gravity molded article. It can be preferably used in all fields requiring processing of vinyl chloride resin, such as sheets, pipes, deformed shapes, and foamed products.

[0053]

The present invention will be described in more detail with reference to the following Examples and Comparative Examples.

The evaluation method is described below.

(Evaluation method) Measurement of specific viscosity (η _sp ) of a solution of 0.4 g of a polymer sample dissolved in 100 ml of benzene: 0.4 g of a polymer sample was dissolved in 100 ml of benzene, and a 30 ° C. water bath was used. The measurement was carried out using a Ubelod type viscometer maintained at a constant temperature.

Evaluation of the composition: The following method was used.

Polyvinyl chloride (average degree of polymerization: 660) 10
3 parts of polymer sample obtained in 0 parts, 1.5 parts of octyltin mercaptide-based stabilizer, 1.5 parts of epoxidized soybean oil
, 1.0 part of butyl stearate and 0.5 part of a polyglycol ester of a fatty acid were evaluated by the following method.

(Gellability) A small kneading tester (Plasticorder manufactured by Brabender, PLE-
331), the mixture was kneaded at a temperature of 150 ° C., and the gelling property was evaluated from the slope of a straight line connecting the points of the minimum torque and the maximum torque in the kneading time versus torque curve. It was determined that the larger the slope, the better the gelling property.

(Transparency) 160 with an 8-inch test roll
After kneading at 5 ° C. × 5 minutes, the mixture was pressed at 170 ° C. × 15 minutes to form a pressed plate having a thickness of 5 mm. Of the obtained press plate,
The total light transmittance and haze were measured according to JIS-6714. The total light transmittance indicates that the larger the number, the better the transparency. Also, the smaller the number, the better the haze.

(Workability) 160 with 8 inch test roll
After kneading at 5 ° C. × 5 minutes, the mixture was pressed at 170 ° C. × 15 minutes to form a pressed plate having a thickness of 1 mm. The elongation of the press plate was measured according to JIS K7113. The dumbbell used was JIS No. 2, the measurement temperature was 100 ° C., and the tensile speed was 200 mm / min. The larger the elongation, the better the processing aid.

The foaming property was determined by mixing 0.6 parts of azodicarbonamide with the above-mentioned blend, and molding at 170 ° C. using a small extruder (2D20C) manufactured by Toyo Seiki Co., Ltd. Was evaluated. It can be said that the lower the specific gravity of the molded body, the better the foamability.

Example 1 An 8 l reactor equipped with a stirrer was charged with 0.8 parts of sodium dioctylsulfosuccinate and 0.05 parts of potassium persulfate previously dissolved in water, and water was further added to reduce the total amount of water to 20 parts.
0 parts. After oxygen was removed from the space and water by flowing nitrogen through the reactor, the contents were heated to 70 ° C. while stirring. Next, a monomer mixture (mixture (A)) consisting of 3 parts of methyl methacrylate (MMA) and 7 parts of butyl acrylate (BA) was dropped into the reactor at a rate of about 20 parts per hour. After completion of the dropwise addition, stirring was continued for 1 hour to substantially complete the polymerization. Thereafter, 72 parts of MMA and butyl methacrylate (BM
A) 1 part of a monomer mixture (mixture (B)) consisting of 18 parts
It was dropped at a rate of about 20 parts per hour. After dropping,
Keep the contents at 70 ° C for 90 minutes, then cool,
I got latex. The polymerization conversion was 99.5%.
The particle diameter of the polymer particles in the latex determined by the turbidity method was 1200 °. The obtained latex is salted out and coagulated with an aqueous solution of calcium chloride, heated to 90 ° C. and heat-treated, and then filtered using a centrifugal dehydrator. Wash with water
The polymer was dried at 50 ° C. for 15 hours using a parallel flow dryer to obtain a white powdery polymer sample (1).

The obtained polymer sample (1) was evaluated by the above method.

Table 1 shows the results.

In the table, MMA is methyl methacrylate,
BA is butyl acrylate, EA is ethyl acrylate, B
MA indicates butyl methacrylate and AN indicates acrylonitrile.

Examples 2 to 4 and Comparative Examples 1 to 3 Polymer samples (2) to (4), (6) and (7) were prepared in the same manner as in Example 1 according to the components and amounts shown in Table 1. I got it. The polymer sample (5) was a one-stage polymer in which the mixture (A) was not polymerized, but was obtained in substantially the same manner as described above. The particle size of the obtained latex was all 1100
１1300 °.

The obtained polymer sample was evaluated by the above method.

Table 1 shows the results.

[0069]

[Table 1]

From Table 1, it can be seen that a monomer mixture containing a predominant amount of methyl methacrylate was added to a copolymer latex obtained by emulsion polymerization of a monomer mixture containing a predominant amount of an alkyl acrylate, followed by polymerization. It can be seen that when the polymer samples (1) to (4) obtained were used, the vinyl chloride resin composition was more excellent in gelling property and workability than the polymer sample (5) which was a one-stage polymer. Further, when the amount of the mixture (A) is smaller than the range of the present invention as in the polymer sample (6), the gelling property is not sufficient. On the other hand, when the amount of the mixture (A) is larger than the range of the present invention as in the polymer sample (7), the gelling property is not changed, but the processability and the transparency are reduced.

Examples 5 to 10 and Comparative Examples 4 and 6 Polymer samples (8) to (16) were obtained in the same manner as in Example 1 according to the components and amounts shown in Table 2. The particle size of the polymer particles in the obtained latex was 1000 to 1300
It was included in the range of Å.

The obtained polymer sample was evaluated by the above-described evaluation method.

Table 2 shows the results.

[0074]

[Table 2]

From the results in Table 2, polymer samples (8) to (1)
When 3) is used, a composition having good gelling properties, transparency and processability can be obtained, but the copolymerization ratio of methacrylic esters and acrylic esters other than methyl methacrylate exceeds the range of the present invention. It can be seen that when the polymer samples (14) and (15) using the equivalents of the mixture (B) which was increased were used, transparency and workability were reduced. When a small amount of a monomer (acrylonitrile) other than methacrylic acid ester and acrylic acid ester (acrylonitrile) is copolymerized as in the polymer sample (13), it does not cause deterioration in physical properties.
As in the polymer sample (16), the composition ratio of the monomer (acrylonitrile) other than the methacrylic acid ester and the acrylic acid ester was set to be 1 equivalent to the mixture (B) over the range of the present invention.
It can be seen that when the content is 0% or more, the gelling property decreases and other physical properties also decrease.

Examples 11 and 12 and Comparative Examples 7 to 10 Polymer samples (17) and (18) and polymer samples (19) to
(22) adjusts the amount of the initiator (potassium persulfate) and the amount of the emulsifier (sodium dioctyl sulfosuccinate) to adjust η _sp
And polymer particles of latex were prepared in the same manner as in Example 1 except that the particle size of the polymer particles was adjusted.

A composition was prepared using the obtained polymer sample, and the transparency and processability were evaluated.

Table 3 shows the results.

[0079]

[Table 3]

From the results shown in Table 3, since the polymer samples (19), (20) and (21) having η _sp of less than 1 cannot obtain sufficient workability, η _sp is 1 It can be seen that it must be greater than or equal to .0.

When polymer samples (17) and (18) were used, even if η _sp was increased, the transparency was hardly reduced and the workability was rather improved, but the equivalent of mixture (A) was not obtained. When polymer samples (5) and (22) that do not exist are used, it can be seen that when η _sp is increased, the transparency is remarkably reduced and the processability is not sufficient.

Examples 13 and 14, Reference Examples 1 and 2 Polymer samples (23) and (24) were prepared using the initiator (potassium persulfate) amount and emulsifier (dioctyl sulfosuccinate sodium).
Was obtained in the same manner as in Example 1 except that the amount of was adjusted to adjust η _sp and the particle size of the polymer particles in the latex.

The evaluation was performed using the obtained polymer sample. In the above evaluation method, the temperature of the 8-inch roll was 150 ° C., the temperature of the press was 160 ° C., and the temperature of the press was 160 ° C. The evaluation was performed by changing the temperature of a small extruder for evaluating foaming properties to 160 ° C.

Table 4 shows the results.

[0085]

[Table 4]

Reference Examples 1 and 2 are the same polymer samples as those used in Examples 1 and 11, and the processing conditions were changed. In the evaluation items of Reference Examples 1 and 2, the processing condition was set to 10
It can be seen that lowering the temperature by ℃ lowers the transparency, workability and the like of those having a high η _sp . On the other hand, in Examples 13 and 14 using the polymer samples (23) and (24) in which the latex particle diameter was 1000 ° or less, the transparency did not decrease even at a high η _sp , and the processability was rather improved. The effect of making the latex particle diameter 1000 ° or less can be seen.

Examples 15 and 16 and Comparative Examples 11 and 12 In order to evaluate the effect of changing the number of parts of the polymer sample (1) used in Example 1 to the composition, the above evaluation method was used. Instead of 3 parts of the combined sample, the number of blending parts shown in Table 5 was used, and the others were evaluated in the same manner as in the above evaluation method.

Table 5 shows the results.

[0089]

[Table 5]

From the results shown in Table 5, the composition containing the polymer sample (1) within the scope of the present invention has good gelling properties, transparency and processability. As described above, when the number of parts is reduced beyond the range of the present invention, sufficient gelling property and workability cannot be obtained. In addition, when the compounding amount of the present invention was used beyond the range of the number of parts as in Comparative Example 12, the molded product was more nonuniform, and a molded product suitable for evaluating transparency and processability could not be obtained. .

[0091]

The composition of the present invention has good gelling properties, as well as good transparency and processability. The composition having such preferable characteristics is a vinyl chloride resin 1
It is produced by adding a small amount of processing aid of 0.1 to 30 parts to 00 parts.

Continued on the front page (72) Inventor Yasushi Nakanishi 3-3-26-202, Nishiakashikita-cho, Akashi-shi, Hyogo (72) Inventor Kadkra Mamor Belgium, 1950 Kleinem, Konin Jin Astrid Lahn 143 (72) Inventor Karin Janssen Belgium Kingdom, 3290 Dest, Dolly Sstraat 2 (72) Inventor Akira Takagi 1-2-13-202, Kotoku-cho, Nada-ku, Kobe-shi, Hyogo (72) Inventor Yasuhiro Miki 881 Kitahara, Himeji-shi, Hyogo

Claims (2)

[Claims] 1. A composition comprising 100 parts by weight of a vinyl chloride resin and 0.1 to 30 parts by weight of a processing aid for a vinyl chloride resin, wherein the processing aid for a vinyl chloride resin is:
Emulsion polymerization of 3 to 30 parts by weight of a mixture (A) of 0 to 50% by weight of methyl methacrylate, 50 to 100% by weight of alkyl acrylate and 0 to 20% by weight of a vinyl monomer copolymerizable therewith. In the presence of the latex obtained, 60 to 100% by weight of methyl methacrylate and 0 to 40% by weight of at least one monomer selected from alkyl acrylate and alkyl methacrylate excluding methyl methacrylate, and A total amount of 70 to 97 parts by weight of a mixture (B) with 0 to 10% by weight of a polymerizable vinyl monomer is 100%.
A polymer obtained by adding and polymerizing so as to be parts by weight,
A vinyl chloride resin composition, wherein a specific viscosity at 30 ° C. of a solution obtained by dissolving 0.4 g of the polymer in 100 ml of benzene is 1 or more. 2. The vinyl chloride resin composition according to claim 1, wherein the latex of the polymer of the processing aid for the vinyl chloride resin has a particle size of 1000 ° or less.